Field effect transistors having multiple effective work functions

ABSTRACT

Selective deposition of a silicon-germanium surface layer on semiconductor surfaces can be employed to provide two types of channel regions for field effect transistors. Anneal of an adjustment oxide material on a stack of a silicon-based gate dielectric and a high dielectric constant (high-k) gate dielectric can be employed to form an interfacial adjustment oxide layer contacting a subset of channel regions. Oxygen deficiency can be induced in portions of the high-k dielectric layer overlying the interfacial adjustment oxide layer by deposition of a first work function metallic material layer and a capping layer and a subsequent anneal. Oxygen deficiency can be selectively removed by physically exposing portions of the high-k dielectric layer. A second work function metallic material layer and a gate conductor layer can be deposited and planarized to form gate electrodes that provide multiple effective work functions.

BACKGROUND

The present disclosure generally relates to semiconductor devices, andparticularly to semiconductor structures including field effecttransistors having multiple effective work functions, and methods ofmanufacturing the same.

Advanced semiconductor circuits employ multiple types of field effecttransistors having different threshold voltages. While methods ofemploying ion implantation to alter the channel doping for the purposeof providing different threshold voltages are known in the art, controlof threshold voltages through ion implantation alone does not provide afull range of variations in the threshold voltage that is desired fromfield effect transistors. Thus, an integration scheme is desired thatcan provide a wider range of threshold voltages for various field effecttransistors.

SUMMARY

Selective deposition of a silicon-germanium surface layer onsemiconductor surfaces can be employed to provide two types of channelregions for field effect transistors. A silicon-based gate dielectriclayer and a high dielectric constant (high-k) dielectric layer can beformed on the channel regions, and an adjustment oxide layer can beformed on a subset of surfaces of the high-k dielectric layer bydeposition and patterning. Employing capping and a drive-in anneal, theadjustment oxide layer can diffuse through the high-k dielectric layerto form an interfacial adjustment oxide layer contacting channelregions. Oxygen deficiency can be induced in portions of the high-kdielectric layer overlying the interfacial adjustment oxide layer bydeposition of a first work function metallic material layer and acapping layer and a subsequent anneal. After removal of the cappinglayer and patterning of the first work function metallic material layer,oxygen deficiency can be selectively removed in physically exposedportions of the high-k dielectric layer. A second work function metallicmaterial layer and a gate conductor layer can be deposited andplanarized to form gate electrodes that provide multiple effective workfunctions over the two types of channel regions.

According to an aspect of the present disclosure, a semiconductorstructure is provided, which includes a first gate dielectric, a firstgate electrode, a second gate dielectric, and a second gate electrode.The first gate dielectric straddles a first semiconductor materialportion and contains a stack of an adjustment oxide layer including asilicate of a metal selected from alkaline earth metals, Group IIIBelements, and rare earth metals and a first high dielectric constant(high-k) gate dielectric including a dielectric metal oxide and having adielectric constant greater than 8.0. The first gate electrode is incontact with the first gate dielectric and contains a first metallicmaterial layer in contact with the first high-k gate dielectric. Thesecond gate electrode straddles a second semiconductor material portionand contains a stack of a semiconductor oxide layer and a second high-kgate dielectric. The first high-k gate dielectric differs in compositionfrom the second high-k gate dielectric by presence of oxygen deficiencyin the first high-k gate dielectric. The second gate electrode is incontact with the second gate dielectric and contains a second metallicmaterial layer in contact with the second high-k gate dielectric.

According to another aspect of the present disclosure, a method offorming a semiconductor structure is provided. At least a firstsemiconductor material portion and a second semiconductor materialportion are formed on a substrate. A first dielectric material stack isformed over the first semiconductor material portion, and a seconddielectric material stack is formed over the second semiconductormaterial portion. The first dielectric material stack includes anadjustment oxide layer that includes a silicate of a metal selected fromalkaline earth metals, Group IIIB elements, and rare earth metals, and afirst portion of a contiguous high dielectric constant (high-k)dielectric layer. The second dielectric material stack includes asemiconductor oxide layer and a second portion of the contiguous high-kdielectric layer. A first metallic material layer and a sacrificialcapping layer are formed on the high-k dielectric layer over the firstand second dielectric material stacks. Oxygen deficiency is induced inthe contiguous high-k dielectric layer employing an anneal in whichoxygen supply into the contiguous high-k dielectric layer is blocked bythe sacrificial capping layer. A top surface of the second portion ofthe contiguous high-k dielectric layer is physically exposed by removinga portion of the first metallic material layer, while a remainingportion of the first metallic material layer is present over the firstsemiconductor material portion. A second metallic material layer isformed directly on the top surface of the second portion of thecontiguous high-k dielectric layer and a top surface of the firstmetallic material layer.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1A is a top-down view of an exemplary semiconductor structure afterformation of various semiconductor material portions on a substrateaccording to an embodiment of the present disclosure.

FIG. 1B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 1A.

FIG. 2A is a top-down view of the exemplary semiconductor structureafter formation and patterning of a dielectric mask layer and selectiveepitaxy that forms semiconductor shell structures according to anembodiment of the present disclosure.

FIG. 2B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 2A.

FIG. 3A is a top-down view of the exemplary semiconductor structureafter removal of the patterned dielectric mask layer according to anembodiment of the present disclosure.

FIG. 3B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 3A.

FIG. 4A is a top-down view of the exemplary semiconductor structureafter formation a disposable gate structure, various source and drainregions, and at least one gate spacer according to an embodiment of thepresent disclosure.

FIG. 4B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 4A.

FIG. 5A is a top-down view of the exemplary semiconductor structureafter formation and patterning of a dielectric mask layer and selectiveepitaxy that forms semiconductor shell structures according to anembodiment of the present disclosure.

FIG. 5B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 5A.

FIG. 6A is a top-down view of the exemplary semiconductor structureafter deposition and planarization of a planarization dielectric layeraccording to an embodiment of the present disclosure.

FIG. 6B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 6A.

FIG. 7A is a top-down view of the exemplary semiconductor structureafter formation of a gate cavity by removal of the disposable gatestructure and deposition of at least one semiconductor oxide layer and acontiguous high dielectric constant (high-k) dielectric layer accordingto an embodiment of the present disclosure.

FIG. 7B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 7A.

FIG. 8A is a top-down view of the exemplary semiconductor structureafter formation and patterning of a dielectric oxide material layeraccording to an embodiment of the present disclosure.

FIG. 8B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 8A.

FIG. 9A is a top-down view of the exemplary semiconductor structureafter formation of first sacrificial capping layers according to anembodiment of the present disclosure.

FIG. 9B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 9A.

FIG. 10A is a top-down view of the exemplary semiconductor structureafter formation of an adjustment oxide layer by an anneal according toan embodiment of the present disclosure.

FIG. 10B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 10A.

FIG. 11A is a top-down view of the exemplary semiconductor structureafter removal of the first sacrificial capping layers according to anembodiment of the present disclosure.

FIG. 11B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 11A.

FIG. 12A is a top-down view of the exemplary semiconductor structureafter formation of a first metallic material layer and a secondsacrificial capping layer according to an embodiment of the presentdisclosure.

FIG. 12B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 12A.

FIG. 13A is a top-down view of the exemplary semiconductor structureafter formation of oxygen vacancies in the contiguous high-k gatedielectric layer according to an embodiment of the present disclosure.

FIG. 13B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 13A.

FIG. 14A is a top-down view of the exemplary semiconductor structureafter removal of the second sacrificial capping layer and patterning ofthe first metallic material layer according to an embodiment of thepresent disclosure.

FIG. 14B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 14A.

FIG. 15A is a top-down view of the exemplary semiconductor structureafter formation of a second metallic material layer according to anembodiment of the present disclosure.

FIG. 15B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 15A.

FIG. 16A is a top-down view of the exemplary semiconductor structureafter formation of gate electrodes according to an embodiment of thepresent disclosure.

FIG. 16B is a vertical cross-sectional view of the exemplarysemiconductor structure along the vertical plane B-B′ in FIG. 16A.

DETAILED DESCRIPTION

As stated above, the present disclosure relates to semiconductorstructures including field effect transistors having multiple effectivework functions, and methods of manufacturing the same. Aspects of thepresent disclosure are now described in detail with accompanyingfigures. Like and corresponding elements mentioned herein andillustrated in the drawings are referred to by like reference numerals.The drawings are not necessarily drawn to scale. As used herein,ordinals such as “first,” “second,” and “third” are employed merely todistinguish similar elements, and different ordinals may be employed todesignate a same element in the specification and/or claims.

As used herein, a field effect transistor refers to any planartransistor having a gate electrode overlying a horizontal planarchannel, any fin field effect transistor having a gate electrode locatedon sidewalls of a semiconductor fin, or any other types of metal-oxidesemiconductor field effect transistor (MOSFETs) and junction fieldeffect transistors (JFETs).

Referring to FIGS. 1A and 1B, an exemplary semiconductor structureaccording to an embodiment of the present disclosure includes varioussemiconductor material portions (30, 40, 52, 62) formed on a substrate(10, 20). The various semiconductor material portions (30, 40, 52, 62)can be patterned from a top semiconductor layer of asemiconductor-on-insulator (SOI) substrate, or can be patterned from anupper portion of a bulk semiconductor substrate. The substrate (10, 20)can be a combination of an insulator layer 20 and a handle substratederived from an SOI substrate, or can be an unpatterned portion of abulk semiconductor substrate.

The various semiconductor material portions (30, 40, 52, 62) includes atleast one semiconductor material. The various semiconductor materialportions (30, 40, 52, 62) can include the same semiconductor material,or can include different materials. The semiconductor material(s) of thevarious semiconductor material portions (30, 40, 52, 62) can be anelemental semiconductor material such as silicon or germanium, asemiconductor alloy including at least one elemental semiconductormaterial such as a silicon-germanium alloy or a silicon-carbon alloy, acompound semiconductor material, and/or an organic semiconductormaterial. The semiconductor material(s) of the various semiconductormaterial portions (30, 40, 52, 62) can be single crystalline. In oneembodiment, the semiconductor material(s) of the various semiconductormaterial portions (30, 40, 52, 62) can be single crystalline silicon.

The height of each semiconductor material portion (30, 40, 52, 62) canbe in a range from 10 nm to 500 nm, although lesser and greater heightscan also be employed. The width of each semiconductor material portion(30, 40, 52, 62) can be in a range from 30 nm to 1,000 nm, althoughlesser and greater widths can also be employed. Each semiconductormaterial portion (30 40, 52, 62) may have the same height, or may havedifferent heights. The length of each semiconductor material portion(30, 40, 52, 62) can be in a range from 100 nm to 10,000 nm, althoughlesser and greater lengths can also be employed. In one embodiment, thesemiconductor material portions (30, 40, 52, 62) can be provided withoutany intervening dielectric material layer thereamongst. In anotherembodiment, a shallow trench isolation layer (not shown) may be providedamong the various semiconductor material portions (30, 40, 52, 62).

In one embodiment, the various semiconductor material portions (30, 40,52, 62) can include a first semiconductor material portion 30 formed ina first device region 100, a second semiconductor material portion 40formed in a second device region 200, a third semiconductor materialportion 52 formed in a third device region 300, and a fourthsemiconductor material portion 62 formed in a fourth device region 400.In one embodiment, the first, second, third, and fourth semiconductormaterial portions (30, 40, 52, 62) can include the same semiconductormaterial, which can be a single crystalline semiconductor material suchas silicon.

In one embodiment, the first, second, third, and fourth semiconductormaterial portions (30, 40, 52, 62) can be semiconductor fins. As usedherein, a semiconductor fin refers to a semiconductor material portionhaving a parallel pair of sidewalls that extend along the lengthwisedirection of the semiconductor material portion. As used herein, alengthwise direction of an element refers to an element along which anaxis of rotation passing through the center of mass of the element hasthe least moment of inertia. The lengthwise direction of eachsemiconductor fin can be along a horizontal direction.

Referring to FIGS. 2A and 2B, a dielectric mask layer 25 can bedeposited on the surfaces of the various semiconductor material portions(30 40, 52, 62), and subsequently patterned to cover one set ofsemiconductor material portions (30, 40), while not covering another setof semiconductor material portions (52, 62). The dielectric mask layer25 includes a dielectric material such as silicon nitride, siliconoxynitride, silicon oxide, a dielectric metal oxide, a dielectric metalnitride, or a combination thereof. The dielectric mask layer 25 can bedeposited, for example, by chemical vapor deposition or atomic layerdeposition. In one embodiment, the first semiconductor material portion30 and the second semiconductor material portion 40 can be covered bythe dielectric mask layer 25 after patterning of the dielectric masklayer 25, and the third semiconductor material portion 52 and the fourthsemiconductor material portion 62 can be physically exposed to anambient after patterning of the dielectric mask layer 25.

In one embodiment, the semiconductor materials of the firsts, second,third, and fourth semiconductor material portions (30, 40, 52, 62) canbe a same semiconductor material, which is herein referred to as a firstsemiconductor material. A semiconductor material different incomposition than the first semiconductor material can be deposited onthe surfaces of the third and fourth semiconductor material portions(52, 62) by selective epitaxy of a semiconductor material having adifferent composition than the first semiconductor material. Forexample, the first semiconductor material can be single crystallinesilicon, and the second semiconductor material can be a singlecrystalline silicon-germanium alloy. A first semiconductor shellstructure 54 can be formed on the sidewall surfaces and the top surfaceof the third semiconductor material portion 52 by selective epitaxialdeposition of the second semiconductor material. A second semiconductorshell structure 64 can be formed on the sidewall surfaces and the topsurface of the fourth semiconductor material portion 62 by selectiveepitaxial deposition of the second semiconductor material. As usedherein, a “shell structure” refers to a structure that laterallyencloses another structure.

The first semiconductor shell structure 54 can be single crystalline,and in epitaxial alignment with the single crystalline firstsemiconductor material of the third semiconductor material portion 52.The first semiconductor shell structure 54 embeds the thirdsemiconductor material portion 52. The second semiconductor shellstructure 64 can be single crystalline, and in epitaxial alignment withthe single crystalline first semiconductor material of the fourthsemiconductor material portion 62. The second semiconductor shellstructure 64 embeds the fourth semiconductor material portion 62. Thecombination of the third semiconductor material portion 52 and the firstsemiconductor shell structure 54 constitutes a first semiconductormaterial stack 50. The combination of the fourth semiconductor materialportion 62 and the second semiconductor shell structure 64 constitutes asecond semiconductor material stack 60.

Referring to FIGS. 3A and 3B, after formation of the first and secondsemiconductor shell structures (54, 64), the dielectric mask layer 25can be removed, for example, by a wet etch. In one embodiment, thedielectric mask layer 25 can be removed selective to the dielectricmaterial of the insulator layer 20.

Referring to FIGS. 4A and 4B, at least one disposable material layer canbe deposited and patterned employing a combination of lithographicmethods and at least one anisotropic etch to form at least onedisposable gate structure (71, 73, 75). In one embodiment, the at leastone disposable material layer can include, from bottom to top, adisposable dielectric layer, a disposable gate material layer, and adisposable cap layer. The disposable dielectric layer includes adielectric material that can be removed selective to the semiconductormaterial portions (30, 40) and the semiconductor material stacks (50,60). For example, the disposable dielectric layer can include siliconoxide, silicon nitride, a dielectric metal oxide, or a combinationthereof. The thickness of the disposable dielectric layer can be in arange from 1 nm to 10 nm, although lesser and greater thicknesses canalso be employed. The disposable gate material layer can include amaterial that can be subsequently removed selective to the dielectricmaterial of the disposable dielectric layer. For example, the disposablegate material layer can include a semiconductor material, amorphouscarbon, an organic material, or a metallic material. The thickness ofthe disposable gate material layer depends on the target height of areplacement gate structure to be subsequently formed, and can be in arange from 100 nm to 500 nm, although lesser and greater heights canalso be employed. The disposable cap layer can include a dielectricmaterial such as silicon nitride. The thickness of the disposable caplayer depends on the height of the semiconductor material portions (30,40) and the semiconductor material stacks (50, 60) if the semiconductormaterial portions (30, 40) and the semiconductor material stacks (50,60) are semiconductor fins, and may otherwise depend on the anticipatederosion during subsequent planarization of a planarization dielectriclayer.

The vertical stack of the disposable dielectric layer, the disposablegate material layer, and the disposable cap layer can be patterned, forexample, by application of a photoresist layer on the top surface of thedisposable cap layer, lithographic patterning of the photoresist layer,and an anisotropic etch that etches the materials of the vertical stackin areas that are not covered by the photoresist layer. The photoresistlayer can be subsequently removed, for example, by ashing. Eachdisposable gate structure (71, 73, 75) can include, from bottom to top,a disposable dielectric portion 71, a disposable gate material portion73, and a disposable gate cap 75. Each disposable dielectric portion 71is a remaining portion of the disposable dielectric layer, eachdisposable gate material portion 73 is a remaining portion of thedisposable gate material layer, and each disposable gate cap 75 is aremaining portion of the disposable gate cap layer. Each disposable gatestructure (71, 73, 75) straddles at least one of the semiconductormaterial portions (30, 40) or the semiconductor material stacks (50,60). A disposable gate structure (71, 73. 75) may straddle only one ofthe semiconductor material portions (30, 40) or the semiconductormaterial stacks (50, 60), or may straddle a plurality of thesemiconductor material portions (30, 40) and/or the semiconductormaterial stacks (50, 60).

A gate spacer 76 including a dielectric material can be optionallyformed around each disposable gate structure (71, 73, 75), for example,by conformal deposition of at least one dielectric material and ananisotropic etch. The at least one dielectric material can includesilicon oxide, silicon nitride, or a combination thereof. While thepresent disclosure is described employing an embodiment in which thegate spacers 76 are formed prior to formation of source regions anddrain region, embodiments are expressly contemplated herein in which atleast a portion of source regions and drain regions is formed prior toformation of the gate spacers 76.

Source regions (3S, 4S, 5S, 6S) and drain regions (3D, 4D, 5D, 6D) canbe formed in the first and second semiconductor material portions (30,40; See FIGS. 3A and 3B) and the first and second semiconductor materialstacks (50, 60; See FIGS. 3A and 3B) employing methods known in the art.A first source region 3S and a first drain region 3D can be formed inthe first semiconductor material portion (3S, 3D, 3B) by introduction ofelectrical dopants of a first conductivity type, which can be p-type orn-type. The sub-portion of the first semiconductor material portion 30into which the electrical dopants of the first conductivity type are notintroduced constitutes a first body region 3B. A surface portion of thefirst body region 3B is a first channel region (not specifically shown).In one embodiment, p-n junctions can be formed between the first bodyregion 3B and the first source and drain regions (3S, 3D).

A third source region 5S and a third drain region 5D can be formed inthe first semiconductor material stack (5S, 5D, 5B, 5C) by introductionof electrical dopants of the first conductivity type. The portion of thefirst semiconductor material stack 50 into which the electrical dopantsof the first conductivity type are not introduced constitutes a thirdbody region (5B, 5C). The portion of the third body region (5B, 5C) thatincludes the second semiconductor material can be a third channel region5C. In one embodiment, p-n junctions can be formed between the thirdbody region (5B, 5C) and the third source and drain regions (5S, 5D). Inone embodiment, the first source region 3S, the third source region 5S,the first drain region 3D, and the third drain region 5D can be formedsimultaneously.

A second source region 4S and a second drain region 4D can be formed inthe second semiconductor material portion (4S, 4D, 4B) by introductionof electrical dopants of a second conductivity type. The secondconductivity type can be the opposite of the first conductivity type.For example, if the first conductivity type is p-type, the secondconductivity type is n-type, and vice versa. The sub-portion of thesecond semiconductor material portion (4S, 4D, 4B) into which theelectrical dopants of the second conductivity type are not introducedconstitutes a second body region 4B. A surface portion of the secondbody region 4B is a first channel region (not specifically shown). Inone embodiment, p-n junctions can be formed between the second bodyregion 4B and the second source and drain regions (4S, 4D).Alternatively, the first body region 3B and/or the second body region 4Bmay be intrinsic.

A fourth source region 6S and a fourth drain region 6D can be formed ineach second semiconductor material portion (6S, 6D, 6B, 6C) byintroduction of electrical dopants of the second conductivity type. Eachportion of the second semiconductor material stack (6S, 6D, 6B, 6C) intowhich the electrical dopants of the second conductivity type are notintroduced constitutes a second body region (6B, 6C). The portion of thefourth body region (6B, 6C) that includes the second semiconductormaterial can be a fourth channel region 6C. In one embodiment, p-njunctions can be formed between the second body region (6B, 6C) and thefourth source and drain regions (6S, 6D). Alternatively, the third bodyregion (5B, 5C) and/or the fourth body region (6B, 6C) may be intrinsic.In one embodiment, the second source region 4S, the fourth source region6S, the second drain region 4D, and the fourth drain region 6D can beformed simultaneously.

Referring to FIGS. 5A and 5B, raised source regions (3R, 4R, 5R, 6R) andraised drain regions (3T, 4T, 5T, 6T) can be optionally formed byselective deposition of doped semiconductor materials. At least onedisposable dielectric masking layer (not shown) may be employed toinduce deposition of semiconductor materials only in desired regions.Specifically, first and third raised source regions (3S, 5S) and firstand fourth raised drain regions (3T, 5T) can be formed on the first andthird source regions (3S, 5S) and the first and third drain regions (3D,5D), respectively. The first and third raised source regions (3S, 5S)and the first and fourth raised drain regions (3T, 5T) can have a dopingof the first conductivity type. Second and fourth raised source regions(4S, 6S) and second and fourth raised drain regions (4T, 6T) can beformed on the second and fourth source regions (4S, 6S) and the secondand fourth drain regions (4D, 6D), respectively. The second and fourthraised source regions (4S, 6S) and the second and fourth raised drainregions (4T, 6T) can have a doping of the second conductivity type.Optionally, metal semiconductor alloy regions (not shown) can be formedon the physically exposed surfaces of the raised source and drainregions (3R, 4R, 5R, 6R, 3T, 4T, 5T, 6T), or, if raised source and drainregions are not formed, on the physically exposed surfaces of the sourceand drain regions (3S, 4S, 5S, 6S, 3D, 4D, 5D, 6D).

Referring to FIGS. 6A and 6B, a planarization dielectric layer 60 isdeposited over the disposable gate structures (71, 73, 75), thesemiconductor material portions (3S, 3D, 3B, 4S, 4D, 4B), and thesemiconductor material stacks (5S, 5D, 5B, 5C, 6S, 6D, 6B, 6C), and canbe subsequently planarized employing the disposable cap portions 75 asstopping layers. The planarization dielectric layer 60 includes adielectric material that may be easily planarized. For example, theplanarization dielectric layer 60 can be composed of a doped silicateglass or an undoped silicate glass (silicon oxide). The planarizationcan be performed, for example, by chemical mechanical planarization(CMP). The planarization dielectric layer 60 laterally surrounds thesemiconductor material portions (3S, 3D, 3B, 4S, 4D, 4B), thesemiconductor material stacks (5S, 5D, 5B, 5C, 6S, 6D, 6B, 6C), and thedisposable gate structure (71, 73, 75).

Referring to FIGS. 7A and 7B, the at least one disposable gate structure(71, 73, 75) can be removed by at least one etch. The at least one etchcan be a recess etch, which can be an isotropic etch or anisotropicetch. The etch processes employed to remove the at least one disposablegate cap 75 and the at least one disposable gate material portion 73 canbe selective to the dielectric materials of the planarization dielectriclayer 60. The etch chemistry employed to remove the at least onedisposable dielectric portion 71 can be selective to the semiconductormaterials of the semiconductor material portions (3S, 3D, 3B, 4S, 4D,4B) and the semiconductor material stacks (5S, 5D, 5B, 5C, 6S, 6D, 6B,6C). Thus, the at least one disposable gate structure (71, 73, 75) canbe removed selective to the planarization dielectric layer 60 and to thesemiconductor material portions (3S, 3D, 3B, 4S, 4D, 4B) and thesemiconductor material stacks (5S, 5D, 5B, 5C, 6S, 6D, 6B, 6C). A gatecavity 79 is formed in each volume from which a disposable gatestructure (71, 73, 75) is removed. Each gate cavity 79 can be laterallyenclosed by a gate spacer 76 and the planarization dielectric layer 60.

A semiconductor oxide layer 82 can be formed directly on the physicallyexposed sidewalls and top surfaces of the semiconductor materialportions (3S, 3D, 3B, 4S, 4D, 4B) and the semiconductor material stacks(5S, 5D, 5B, 5C, 6S, 6D, 6B, 6C) within the gate cavity 79. Thesemiconductor oxide layer 82 is a layer of a semiconductor oxidematerial, and may be formed as a single contiguous layer, for example,by deposition of a semiconductor oxide material by a conformaldeposition method, or may be formed as disjoined semiconductor oxideportions, for example, by thermal oxidation or plasma oxidation of thesurface portions of the semiconductor material portions (3S, 3D, 3B, 4S,4D, 4B) and the semiconductor material stacks (5S, 5D, 5B, 5C, 6S, 6D,6B, 6C) within the gate cavity 79. As used herein, a semiconductor oxiderefers to a dielectric oxide or a dielectric oxynitride of asemiconductor material. Exemplary semiconductor oxides include siliconoxide, silicon oxynitride, an oxide of a silicon-germanium alloy, and anoxynitride of a silicon-germanium alloy. The thickness of thesemiconductor oxide layer 82 can be in a range from 0.5 nm to 2.0 nm,although lesser and greater thicknesses can also be employed.

A high dielectric constant (high-k) dielectric layer 84 can be formed asa contiguous dielectric layer directly on the surfaces of thesemiconductor oxide layer 82. The high-k dielectric layer 84 includes amaterial commonly known as a “high dielectric constant material.” A“high dielectric constant material,” or a “high-k dielectric material,”herein refers to a dielectric material having a dielectric constantgreater than 8.0. In one embodiment, the high-k dielectric layer 84 caninclude a dielectric metal oxide, which is a high-k material containinga metal and oxygen. Dielectric metal oxides can be deposited by methodswell known in the art including, for example, chemical vapor deposition(CVD), physical vapor deposition (PVD), molecular beam deposition (MBD),pulsed laser deposition (PLD), liquid source misted chemical deposition(LSMCD), atomic layer deposition (ALD), etc. Exemplary high-k dielectricmaterial include HfO₂, ZrO₂, La₂O₃, Al₂O₃, TiO₂, SrTiO₃, LaAlO₃, Y₂O₃,HfO_(x)N_(y), ZrO_(x)N_(y), La₂O_(x)N_(y), Al₂O_(x)N_(y), TiO_(x)N_(y),SrTiO_(x)N_(y), LaAlO_(x)N_(y), Y₂O_(x)N_(y), a silicate thereof, and analloy thereof. Each value of x is independently from 0.5 to 3 and eachvalue of y is independently from 0 to 2. The thickness of the high-kdielectric layer 84, as measured at sidewalls of the semiconductormaterial portions (3S, 3D, 3B, 4S, 4D, 4B) or at sidewalls of thesemiconductor material stacks (5S, 5D, 5B, 5C, 6S, 6D, 6B, 6C), can bein a range from 0.9 nm to 10 nm, although lesser and greater thicknessescan also be employed. The high-k dielectric layer 84 can be formed, forexample, by thermal oxidation, thermal nitridation, plasma oxidation,plasma nitridation, chemical vapor deposition (CVD), atomic layerdeposition (ALD), liquid phase deposition (LPD), or other depositionmethods known in the art.

Referring to FIGS. 8A and 8B, a dielectric oxide material layer 83 canbe formed as a contiguous layer on the surfaces of the high-k dielectriclayer 84. The dielectric oxide material layer 83 includes a dielectricoxide of an alkaline earth element, a dielectric oxide of a Group IIIBelement, a dielectric oxide of a Lanthanide element, a dielectric oxideof an alloy of at least two alkaline earth elements, a dielectric oxideof an alloy of at least two Group IIIB elements, a dielectric oxide ofan alloy of at least two Lanthanide elements, or an alloy thereof. Forexample, the dielectric oxide material layer 83 can include scandiumoxide, yttrium oxide, magnesium oxide, strontium oxide, barium oxide,lanthanum oxide, lutetium oxide, dysprosium oxide, or an alloy thereof.The dielectric oxide material layer 83 can be deposited by methods wellknown in the art including, for example, chemical vapor deposition(CVD), physical vapor deposition (PVD), molecular beam deposition (MBD),pulsed laser deposition (PLD), liquid source misted chemical deposition(LSMCD), atomic layer deposition (ALD), etc. The thickness of thedielectric oxide material layer 83 can be in a range from 0.3 nm to 1.5nm, although lesser and greater thicknesses can also be employed. Thedielectric oxide material layer 83, as initially formed, covers theentire area of the high-k dielectric layer 84.

In one embodiment, the dielectric oxide material layer 83 can consist ofan oxide of at least one elemental metal that is not present within thehigh-k dielectric layer 84. For example, the high-k dielectric layer 84can consist essentially of HfO₂, ZrO₂, Al₂O₃, TiO₂, HfO_(x)N_(y),ZrO_(x)N_(y), Al₂O_(x)N_(y), TiO_(x)N_(y), a silicate thereof, or analloy thereof, and the dielectric oxide material layer 83 can consist ofan at least one elemental metal selected from alkaline earth elements,Sc, Y, and Lanthanide elements.

A first photoresist layer 47 is applied over the dielectric oxidematerial layer 83, and is lithographically patterned to cover thedielectric oxide material layer 83 in the first device region 100 and inthe third device region 300, while the portions of the dielectric metaloxide material layer 83 in the second device region 200 and the fourthdevice region 400 are physically exposed to the ambient, i.e., notcovered by a remaining portion of the first photoresist layer 47. Anisotropic etch can be performed to etch the dielectric oxide material ofthe dielectric oxide material layer 83 in the second and fourth deviceregions (200, 400). Portions of the dielectric oxide material layer 83are removed from above the second semiconductor material portion (4S,4D, 4B) and the from above the fourth semiconductor material portion(6S, 6D, 6B, 6C).

A stack including a layer of a semiconductor oxide material (i.e., thesemiconductor oxide layer 82), the contiguous high-k dielectric layer84, and the dielectric oxide material layer 83 is formed on varioussemiconductor material portions (3S, 3D, 3B, 4S, 4D, 4B) and thesemiconductor material stacks (5S, 5D, 5B, 5C, 6S, 6D, 6B, 6C). The topsurfaces and outer sidewall surfaces of the high-k dielectric layer 84are physically exposed to the ambient in the second and fourth deviceregions (200, 400). The first photoresist layer 47 is subsequentlyremoved selective to the dielectric oxide material layer 83 and thehigh-k dielectric layer 84, for example, by ashing.

Referring to FIGS. 9A and 9B, first sacrificial capping layers (87, 89)can be formed on the top surface of the dielectric oxide material layer83 and the high-k dielectric layer 84. As used herein, a “sacrificial”element is a disposable element that is subsequently removed. The firstsacrificial capping layers (87, 89) include at least one material thatprevents loss of the material in the dielectric oxide material layer 83to an anneal ambient during a subsequent anneal process to be performedon the exemplary semiconductor structure. In one embodiment, the firstsacrificial capping layers (87, 89) can include a first sacrificialmetallic material layer 87 and a first sacrificial semiconductor layer89. In an illustrative example, the first sacrificial metallic materiallayer 87 can include a metallic nitride such as titanium nitride, andthe first sacrificial semiconductor layer 89 includes a semiconductormaterial such as amorphous silicon or polysilicon. The thickness of thefirst sacrificial metallic material layer 87 can be in a range from 3 nmto 20 nm, and the thickness of the first sacrificial semiconductor layer89 can be in a range from 3 nm to 20 nm, although lesser and greaterthicknesses can be employed for each of the first sacrificial metallicmaterial layer 87 and the first sacrificial semiconductor layer 89.While the present disclosure is described employing an embodiment inwhich a plurality of layers is present within the first sacrificialcapping layers (87, 89), embodiments are contemplated herein in which asingle sacrificial capping layer is employed in lieu of the plurality ofsacrificial capping layers.

Referring to FIGS. 10A and 10B, the exemplary semiconductor structure isannealed at an elevated temperature to induce diffusion of the materialof the dielectric oxide material layer 83 through the high-k dielectriclayer 84 and into the semiconductor oxide layer 82 within the first andthird device regions (100, 300). The presence of the first sacrificialcapping layers (87, 89) prevents loss of the dielectric oxide materialin the dielectric oxide material layer 83 to an anneal ambient duringthe anneal process by blocking diffusion of the dielectric oxidematerial through the first sacrificial capping layers (87, 89). Further,the semiconductor oxide layer 82 provides a gettering effect for thedielectric oxide material that diffuses through the high-k dielectriclayer 84. Incorporation of the dielectric oxide material into theportions of the layer of the semiconductor oxide material (i.e., thesemiconductor oxide layer 83) leads to modification of the compositionof the portion of the layer of the semiconductor oxide material withinthe first and third device regions (100, 300). Specifically, thedielectric oxide material originating from the dielectric oxide materiallayer 83 prior to the anneal becomes incorporated during the anneal intothe underlying portion of the layer of the semiconductor oxide materialwithin the first and third device regions (100, 300) to form anadjustment oxide layer 81. If the semiconductor oxide layer 82 includesan oxide of a semiconductor material containing silicon (such assilicon, a silicon-germanium alloy, and a silicon-carbon alloy), theadjustment oxide layer 81 includes a silicate of the at least onenon-oxygen element contained in the dielectric oxide material layer 83.

The elevated temperature and duration of the anneal process can beselected to provide sufficient diffusion for the material of thedielectric oxide material layer 83, and to optimize formation of theadjustment oxide layer 81. In one embodiment, the elevated temperatureof the anneal process can be in a range from 700° C. to 1,100° C. Inanother embodiment, the elevated temperature of the anneal process canbe in a range from 800° C. to 1,000° C. The duration of the annealprocess can be in a range from 10 seconds to 2 hours. In general, ashorter duration of the anneal process corresponds to a higher annealtemperature.

The anneal process forms a first dielectric material stack (81, 84) overthe first semiconductor material portion (3S, 3D, 3B) and the thirdsemiconductor material portion (5S, 5D, 5B, 5C), and forms a seconddielectric material stack (82, 84) over the second semiconductormaterial portion (4S, 4D, 4B) and the second semiconductor materialstack (6S, 6D, 6B, 6C). In one embodiment, the first dielectric materialstack (81, 84) can include an adjustment oxide layer 81 containing asilicate of a metal selected from alkaline earth metals, Group IIIBelements, and rare earth metals, and a first portion of a contiguoushigh dielectric constant (high-k) dielectric layer (i.e., the high-kdielectric layer 82), and the second dielectric material stack (82,84)including a semiconductor oxide layer 82 and a second portion of thecontiguous high-k dielectric layer.

In one embodiment, the dielectric oxide material layer 83 as formed at aprocessing step of FIGS. 8A and 8B can consist of an oxide of at leastone metal that is not present in the high-k dielectric layer 84, and thesemiconductor oxide layer 82 in the second and fourth device regions(200, 400) does not include any of the at least one metal present in thedielectric oxide material layer 83. The adjustment oxide layer 81 in thefirst and third device regions (100, 300) can include a silicate of theat least one metal in the dielectric oxide material layer 83, and thesemiconductor oxide layer 82 in the second and fourth device regions(200, 400) does not include any of the at least one metal present withinthe silicate of the adjustment oxide layer 81. The first portion of thehigh-k dielectric layer 84 within the first and third device regions(100, 300) can include the at least one metal present within thesilicate of the adjustment oxide layer 81 at a lesser atomicconcentration than in the adjustment oxide layer 81. In one embodiment,the atomic concentration of the at least one metal (that is presentwithin the silicate of the adjustment oxide layer 81) within the firstportion of the high-k dielectric layer 84 over the first and thirddevice regions (100, 300) can be less than one half of the atomicconcentration of the at least one metal within the adjustment oxidelayer 81. In another embodiment, the atomic concentration of the atleast one metal within the first portion of the high-k dielectric layer84 over the first and third device regions (100, 300) can be less than20% of the atomic concentration of the at least one metal within theadjustment oxide layer 81.

Referring to FIGS. 11A and 11B, the first sacrificial capping layers(87, 89) can be removed by at least one etch process. Each of the atleast one etch process can be an isotropic etch process. Removal of thefirst sacrificial capping layers (87, 89) can be performed selective tothe high-k dielectric layer 84, i.e., without etching the high-kdielectric layer 84 in any significant amount.

Referring to FIGS. 12A and 12B, a first metallic material layer 92 and asecond sacrificial capping layer 93 are formed on the surfaces of thehigh-k dielectric layer 84 and over the first and second dielectricmaterial stacks (81, 82, 84). In one embodiment, the first metallicmaterial layer 92 can be a first work function material layer thatcontrols the work functions of the semiconductor devices to be formedemploying the first semiconductor material portion (3S, 3D, 3B) and thefirst semiconductor material stack (5S, 5D, 5B, 5C). In one embodiment,the first metallic material layer 92 can include a conductive metallicnitride such as TiN, TaN, WN, or an alloy thereof. In one embodiment,the first metallic material layer 92 can be composited of TiN, which canfunction as a balance band edge work function material if not annealedat an elevated temperature and can function as a conduction band edgework function when annealed at an elevated temperature.

The first metallic material layer 92 can be deposited, for example, bychemical vapor deposition (CVD), atomic layer deposition (ALD), orphysical vapor deposition (PVD). The first metallic material layer 92can be deposited as a conformal layer, and the thickness of the firstmetallic material layer 92 can be in a range from 2 nm to 20 nm,although lesser and greater thicknesses can also be employed.

The second sacrificial capping layer 93 can include a semiconductormaterial such as amorphous silicon, an amorphous silicon-germaniumalloy, polysilicon, or a silicon-containing polycrystalline alloy. Thethickness of the second sacrificial capping layer 93 can be in a rangefrom 5 m to 50 nm, although lesser and greater thicknesses can also beemployed.

Referring to FIGS. 13A and 13B, an anneal process is performed on theexemplary semiconductor structure to form oxygen deficiency in thehigh-k dielectric layer 84. During the anneal process, any oxygen supplyfrom the anneal ambient into the high-k dielectric layer 84 is blockedby the second sacrificial capping layer 93. Due to loss of oxygen atomsto the adjustment oxide layer 81 and the semiconductor oxide layer 82during the anneal process, oxygen vacancies are formed in the high-kgate dielectric layer 84 during the anneal. The high-k dielectric layer82 in a state that includes oxygen vacancies after the anneal process isherein referred to as an oxygen-deficient high-k dielectric layer 94,which is a state of the contiguous high-k dielectric material layer 84in which the dielectric oxide of at least one metallic element hasbecome non-stoichiometric, and specifically, oxygen deficient. Theconcentration of the oxygen deficiency can be in a range from1.0×10¹³/cm³ to 1.0×10¹⁵/cm³, although lesser and greater concentrationsof oxygen deficiency can also be employed.

The anneal can be performed at a temperature greater than 400° C. Theanneal can change the effective work function of the first metallicmaterial layer 92. For example, if the first metallic material layer 92includes a conductive metallic nitride such as TiN, the anneal canchange the effective work function of the first metallic material layerto provide a conduction band edge work function, i.e., a work functionthat is closer to the conduction band edges of the first and secondsemiconductor materials in the semiconductor material portions (3S, 3D,3B, 4S, 4D, 4B) and the semiconductor material stacks (5S, 5D, 5B, 5C,6S, 6D, 6B, 6C).

Referring to FIGS. 14A and 14B, the second sacrificial capping layer 93can be removed selective to the first metallic material layer 92. Anisotropic etch or an anisotropic etch can be employed to remove thesecond sacrificial capping layer 93.

A second photoresist layer 57 is applied over the first metallicmaterial layer 92, and is lithographically patterned to cover the firstdevice region 100 and the third device region 300, while the portions ofthe first metallic material layer 92 in the second device region 200 andthe fourth device region 400 are not covered by the second photoresistlayer 57. The physically exposed portions of the first metallic materiallayer 92 is removed from the second device region 200 and the fourthdevice region by an etch, which can be an isotropic etch or ananisotropic etch. The etch that removes the physically exposed portionsof the first metallic material layer 92 can be selective to thedielectric material of the oxygen-deficient high-k dielectric layer 94.

The first metallic material layer 92 is thus patterned such thatremaining portions of the first metallic material layer 92 are presentin the first and third device regions (100, 300), and are not present inthe second and fourth device regions (200, 400). A top surface of asecond portion of the oxygen-deficient high-k dielectric layer 94becomes physically exposed by removal of a portion of the first metallicmaterial layer 92 from the second and fourth device regions (200, 400),while a remaining portion of the first metallic material layer 92 ispresent over the first semiconductor material portion (3S, 3D, 3B) andthe first semiconductor material stack (4S, 4D, 4B, 4C).

In one embodiment, the oxygen deficiency in the second portion of theoxygen-deficient high-k dielectric layer 94 can be cured by exposing thetop surface of the second portion of the high-k dielectric layer 94. Inthis case, the portions of the oxygen-deficient high-k dielectric layer94 within the second and fourth device regions (200, 400) are exposed tothe ambient of the etch, and/or can be subsequently exposed to anotherambient such as air. The portions of the oxygen-deficient high-kdielectric layer 94 in the second and fourth device regions (200, 400)are exposed to an oxygen-containing ambient during, or after, the etchprocess that removes the physically exposed portions of the firstmetallic material layer 92. Oxygen atoms from the oxygen-containingambient diffuse into the physically exposed portions of theoxygen-deficient high-k dielectric layer 94 within the second and fourthdevice regions (200, 400) to remove the oxygen vacancies therein. Thus,the portions of the oxygen-deficient high-k dielectric layer 94 withinthe second and fourth device regions (200, 400) can lose oxygenvacancies. The resulting high-k dielectric material within the secondand fourth device regions (200, 400) in which oxygen deficiency has beencured is herein referred to as a high-k dielectric layer 84, which hasthe same composition as the high-k dielectric layer 84 as formed at theprocessing steps of FIGS. 7A and 7B. The second photoresist layer 57 canbe removed selective to the first metallic material layer 92 and thehigh-k dielectric layer 84, for example, by ashing.

Referring to FIGS. 15A and 15B, a second metallic material layer 96 canbe formed on the surfaces of the high-k dielectric layer 84 and thefirst metallic material layer 92. In one embodiment, the second metallicmaterial layer 96 can be a second work function material layer thatcontrols the work functions of the semiconductor devices to be formedemploying the second semiconductor material portion (4S, 4D, 4B) and thesecond semiconductor material stack (6S, 6D, 6B, 6C). In one embodiment,the second metallic material layer 96 can include a conductive metallicnitride such as TiN, TaN, WN, or an alloy thereof. In one embodiment,the second metallic material layer 96 can be composited of TiN, whichcan function as a balance band edge work function material provided thatthe material is not subsequently subjected to an anneal at a temperaturegreater than 400° C.

The second metallic material layer 96 can be deposited, for example, bychemical vapor deposition (CVD), atomic layer deposition (ALD), orphysical vapor deposition (PVD). The second metallic material layer 96can be deposited as a conformal layer, and the thickness of the secondmetallic material layer 96 can be in a range from 2 nm to 20 nm,although lesser and greater thicknesses can also be employed.

Referring to FIGS. 16A and 16B, at least one conductive materialdirectly on the second metallic material layer. The at least oneconductive material can include a doped semiconductor material and/or ametallic material. For example, the at least one conductive material caninclude Al, W, Cu, Ag, Au, alloys thereof, or combinations thereof. Theat least one conductive material can be deposited, for example, byphysical vapor deposition (PVD), chemical vapor deposition (CVD), and/orelectroplating.

Portions of the at least one conductive material, the first and secondmetallic material layers (92, 96), the oxygen-deficient high-kdielectric layer 94 (which is a high-k dielectric layer including oxygenvacancies), the high-k dielectric layer 84, the adjustment oxide layer81, and the semiconductor oxide layer 82 located above the horizontalplane including the top surface of the planarization dielectric layer 60can be removed by a planarization process. The planarization process canbe a chemical mechanical planarization (CMP) process. Each remainingportions of the at least one conductive material constitutes a gateelectrode portion 98.

The exemplary semiconductor structure includes a first field effecttransistor located within the first device region 100, a second fieldeffect transistor located within the second device region 200, a thirdfield effect transistor located within the third device region 300, anda fourth field effect transistor located within the fourth device region400.

The first field effect transistor includes a first gate dielectric,which includes portions of the adjustment oxide layer 81 and theoxygen-deficient high-k dielectric layer 94 in the first device region100. The first gate dielectric (81, 94) straddles the firstsemiconductor material portion (3S, 3D, 3B), and can contain a stack ofan adjustment oxide layer 81 including a silicate of a metal selectedfrom alkaline earth metals, Group IIIB elements, and rare earth metals,and can further contain a first high dielectric constant (high-k) gatedielectric including a dielectric metal oxide and having a dielectricconstant greater than 8.0. The first field effect transistor furtherincludes a first gate electrode (92, 96, 98) in contact with the firstgate dielectric (81, 94) and containing a first metallic material layer92 that is in contact with the first high-k gate dielectric, which is aportion of the oxygen-deficient high-k dielectric layer 94 in the firstdevice region 100.

The second field effect transistor includes a second gate dielectric(82, 84), which includes portions of the semiconductor oxide layer 82and the high-k dielectric layer 84 within the second device region 200.The second gate dielectric (82, 84) straddles a second semiconductormaterial portion (4S, 4D, 4B) and containing a stack of a semiconductoroxide layer 82 and a second high-k gate dielectric, which is a portionof the high-k dielectric layer 84 within the second device region 200.The first high-k gate dielectric 94 can differ in composition from thesecond high-k gate dielectric 84 by presence of oxygen deficiency in thefirst high-k gate dielectric 94. The second field effect transistorfurther includes a second gate electrode (96, 98) in contact with thesecond gate dielectric 84 and containing a second metallic materiallayer 96 that is in contact with the second high-k gate dielectric 84.

In one embodiment, the second high-k gate dielectric 96 does not includethe metal in the silicate contained within the adjustment oxide layer81. In one embodiment, the first high-k gate dielectric 84 can includethe metal within the silicate of the adjustment oxide layer 81 at alesser concentration than the adjustment oxide layer 81. In oneembodiment, the first metallic material layer 92 and the second metallicmaterial layer 96 can differ from each other in at least one ofthickness and composition.

The third field effect transistor includes a third gate dielectric,which includes portions of the adjustment oxide layer 81 and theoxygen-deficient high-k dielectric layer 94 in the third device region300. The third gate dielectric (81, 94) straddles the firstsemiconductor material stack (5S, 5D, 5B, 5C), and contains a stack ofanother adjustment oxide layer (which is a portion of the adjustmentoxide layer 81 within the third device region 300) and a third high-kgate dielectric (i.e., the portion of the oxygen-deficient high-kdielectric layer 94 within the third device region 300) that includesthe same dielectric metal oxide as the first high-k gate dielectric. Thefirst semiconductor material stack (5S, 5D, 5B, 5C) includes a firstsemiconductor shell structure 54 (See FIG. 2B) embedding, and inepitaxial alignment with, a third semiconductor material portion 52 (SeeFIG. 2B). The third field effect transistor further includes a thirdgate electrode, which includes the portions of the first and secondmetallic material layers (92, 96) and the gate electrode portion 98within the third device region 300. The third gate electrode (92, 96,98) is in contact with the third gate dielectric (81, 94) and contains alayer of a metallic material, which is a portion of the first metalliclayer 92 and has the same composition and thickness as the firstmetallic material layer 92 within the first device region 100. The layerof the metallic material in the third gate electrode (92, 96, 98) is incontact with the third high-k gate dielectric (81, 94).

The fourth field effect transistor includes a fourth gate dielectric,which includes portions of the semiconductor oxide layer 82 and thehigh-k dielectric layer 84 within the fourth device region 400. Thefourth gate dielectric (82, 84) straddles a second semiconductormaterial stack (6S, 6D, 6B, 6C), and contains a stack of anothersemiconductor oxide layer (which is a portion of the semiconductor oxidelayer 82 in the fourth device region 400) and a fourth high-k gatedielectric (i.e., the portion of the high-k dielectric layer 84 withinthe fourth device region 400) having the same composition and thicknessas the second high-k gate dielectric (82, 84) in the second deviceregion 200. The second semiconductor material stack (6S, 6D, 6B, 6C)includes a second semiconductor shell structure 64 embedding, and inepitaxial alignment with, a fourth semiconductor material portion 62.

The first high-k gate dielectric 94 of the first field effect transistorand the second high-k gate dielectric 84 of the second field effecttransistor can include dielectric metal oxides of a same metal, anddiffer in composition by presence of a doping by at least one elementalmetal that is present within the adjustment oxide layer 81 within thefirst high-k gate dielectric 94 and by absence of the at least oneelemental metal that is present within the adjustment oxide layer 81within the second high-k gate dielectric 84.

The first gate electrode (92, 96, 98) can include a metallic materiallayer, i.e., a portion of the second metallic material layer 96, whichhas the same composition and thickness as the portion of the secondmetallic material layer 96 in the second device region 200. The secondmetallic layer 96 within the first gate electrode (92, 96, 98) is incontact with the first metallic material layer 92. Each of the first andsecond gate electrodes includes a conductive material in contact with aportion of the second metallic material layer 96.

The multiple field effect transistors of the present disclosure canprovide multiple threshold voltages by the various combinations of thefirst metallic layer 92 and the second metallic layer 96 as the workfunction material layer, i.e., a material layer that determines the workfunction of a field effect transistor. Further, the combination of asemiconductor material portion and a semiconductor material stack havingtwo different semiconductor materials at the channel regions underlyingthe gate electrodes provides additional changes in the threshold voltagefor turning on the respective field effect transistors. The combinationof an adjustment oxide layer 81 and an oxygen-deficient high-kdielectric layer provides an additional shift in the work functionlevels of the first and third field effect transistors with respect thesecond and fourth field effect transistors. The above properties can becombined to provide n-type field effect transistors having differentthreshold voltages in the first and third field effect transistors,while providing p-type field effect transistors having differentthreshold voltages in the second and fourth field effect transistors.

While the disclosure has been described in terms of specificembodiments, it is evident in view of the foregoing description thatnumerous alternatives, modifications and variations will be apparent tothose skilled in the art. Each of the various embodiments of the presentdisclosure can be implemented alone, or in combination with any otherembodiments of the present disclosure unless expressly disclosedotherwise or otherwise impossible as would be known to one of ordinaryskill in the art. Accordingly, the disclosure is intended to encompassall such alternatives, modifications and variations which fall withinthe scope and spirit of the disclosure and the following claims.

What is claimed is:
 1. A semiconductor structure comprising: a firstgate dielectric straddling a first semiconductor material portion andcontaining a stack of an adjustment oxide layer including a silicate ofa metal selected from alkaline earth metals, Group IIIB elements, andrare earth metals and a first high dielectric constant (high-k) gatedielectric including a dielectric metal oxide and having a dielectricconstant greater than 8.0; a first gate electrode in contact with saidfirst gate dielectric and containing a first metallic material layer incontact with said first high-k gate dielectric; a second gate electrodestraddling a second semiconductor material portion and containing astack of a semiconductor oxide layer and a second high-k gatedielectric, wherein said first high-k gate dielectric differs incomposition from said second high-k gate dielectric by presence ofoxygen deficiency in said first high-k gate dielectric; and a secondgate electrode in contact with said second gate dielectric andcontaining a second metallic material layer in contact with said secondhigh-k gate dielectric.
 2. The semiconductor structure of claim 1,wherein said second high-k gate dielectric does not include said metalin said silicate.
 3. The semiconductor structure of claim 2, whereinsaid first high-k gate dielectric includes said metal at a lesserconcentration than said adjustment oxide layer.
 4. The semiconductorstructure of claim 1, wherein said first metallic material layer andsaid second metallic material layer differ from each other in at leastone of thickness and composition.
 5. The semiconductor structure ofclaim 1, further comprising a third gate dielectric straddling asemiconductor material stack and containing a stack of anotheradjustment oxide layer and a third high-k gate dielectric including saiddielectric metal oxide, wherein said semiconductor material stackcomprises a semiconductor shell structure embedding, having a differentcomposition from, and in epitaxial alignment with, a third semiconductormaterial portion.
 6. The semiconductor structure of claim 5, furthercomprising a third gate electrode in contact with said third gatedielectric and containing a layer of a metallic material having a samecomposition and thickness as said first metallic material layer and incontact with said third high-k gate dielectric.
 7. The semiconductorstructure of claim 5, further comprising a fourth gate dielectricstraddling another semiconductor material stack and containing a stackof another semiconductor oxide layer and a fourth high-k gate dielectrichaving a same composition and thickness as said second high-k gatedielectric, wherein said another semiconductor material stack comprisesanother semiconductor shell structure embedding, having a differentcomposition from, and in epitaxial alignment with, a fourthsemiconductor material portion.
 8. The semiconductor structure of claim1, wherein said first high-k gate dielectric and said second high-k gatedielectric include dielectric metal oxides of a same metal.
 9. Thesemiconductor structure of claim 1, wherein said first gate electrodefurther comprises another metallic material layer having a samecomposition and thickness as said second metallic material layer and incontact with said first metallic material layer.
 10. The semiconductorstructure of claim 1, wherein each of said first and second gateelectrodes further comprises a conductive material in contact with saidanother metallic material layer and said second metallic material layer,respectively.
 11. A method of forming a semiconductor structurecomprising: forming at least a first semiconductor material portion anda second semiconductor material portion on a substrate; forming a firstdielectric material stack over said first semiconductor material portionand a second dielectric material stack over said second semiconductormaterial portion, said first dielectric material stack comprising anadjustment oxide layer including a silicate of a metal selected fromalkaline earth metals, Group IIIB elements, and rare earth metals and afirst portion of a contiguous high dielectric constant (high-k)dielectric layer, and said second dielectric material stack comprising asemiconductor oxide layer and a second portion of said contiguous high-kdielectric layer; forming a first metallic material layer and asacrificial capping layer on said high-k dielectric layer over saidfirst and second dielectric material stacks; inducing oxygen deficiencyin said contiguous high-k dielectric layer employing an anneal in whichoxygen supply into said contiguous high-k dielectric layer is blocked bysaid sacrificial capping layer; physically exposing a top surface ofsaid second portion of said contiguous high-k dielectric layer byremoving a portion of said first metallic material layer, while aremaining portion of said first metallic material layer is present oversaid first semiconductor material portion; and forming a second metallicmaterial layer directly on said top surface of said second portion ofsaid contiguous high-k dielectric layer and a top surface of said firstmetallic material layer.
 12. The method of claim 11, further comprisingcuring oxygen deficiency in said second portion of said contiguoushigh-k dielectric layer by exposing said top surface of said secondportion of said contiguous high-k dielectric layer prior to formation ofsaid second metallic material layer.
 13. The method of claim 11, furthercomprising: forming a stack including a layer of a semiconductor oxidematerial, said contiguous high-k dielectric layer, and a dielectricoxide material layer on said first and second semiconductor materialportions, said layer of said semiconductor oxide material including saidsemiconductor oxide layer; and annealing said stack employing at leastanother sacrificial capping layer, wherein a material of said dielectricoxide material layer diffuses through said high-k dielectric layer intoan underlying portion of said layer of said semiconductor oxide materialto form said adjustment oxide layer.
 14. The method of claim 13, furthercomprising removing a portion of said dielectric oxide material layerfrom above said second semiconductor material portion prior to formationof said at least another sacrificial capping layer.
 15. The method ofclaim 11, further comprising depositing at least one conductive materialdirectly on said second metallic material layer.
 16. The method of claim15, further comprising: forming a planarization dielectric layer oversaid first semiconductor material portion and said second semiconductormaterial portion prior to formation of said first and second dielectricmaterial stacks; and removing portions of said at least one conductivematerial and said first and second metallic material layers from above ahorizontal plane including a top surface of said planarizationdielectric layer.
 17. The method of claim 11, further comprising:forming a third semiconductor material portion comprising a samematerial as said first and second semiconductor material portions onsaid substrate; forming a semiconductor shell structure on said thirdsemiconductor material portion by selective epitaxial deposition of asemiconductor material having a different composition than said thirdsemiconductor material portion; and forming a third dielectric materialstack having a same composition as said first dielectric material stackover said third semiconductor material portion.
 18. The method of claim17, wherein said first metallic material layer is deposited on saidthird dielectric material stack, and another remaining portion of saidfirst metallic material layer is present over said third dielectricmaterial stack after removal of said portion of said first metallicmaterial layer.
 19. The method of claim 18, further comprising: forminga fourth semiconductor material portion comprising said same material onsaid substrate; forming another semiconductor shell structure on saidthird semiconductor material portion by said selective epitaxialdeposition; and forming a fourth dielectric material stack having a samecomposition as said second dielectric material stack over said fourthsemiconductor material portion.
 20. The method of claim 19, wherein saidfirst metallic material layer is deposited on said fourth dielectricmaterial stack, and is removed from above said fourth semiconductormaterial portion at a time of removal of said portion of said firstmetallic material layer.